Phthalocyanine dyestuffs



United States Patent G 3,657,873 PHTHALOCYANINE DYESTUFFS Andr Pugin and Jakob Bindler, Riehen, near Basel, Switzerland, assignors to J. R. Geigy A.-G., Basel, Switzerland No Drawing. Filed Dec. 9, 1960, Ser. No. 74,784 Claims priority, application Switzerland Dec. 10, 1959 6 Claims. (Cl. 260-3145) The present invention concerns water insoluble dyestuffs of the phthalocyanine series, processes for the production thereof, their use for the production of inks, in particular of inks for ball point pens and stamp pads and, as industrial product, the inks produced with the aid of these dyestuffs.

The new dyestuffs correspond to the general formula 1 2) m 3 n] 2 n In this formula:

Fe is the radical of a phthalocyanine. This is either metal-free or, more advantageously, metal-containing, in particular, heavy metal-containing and, principally, containing copper. In addition to the sulphonyl substituents, the benzo radicals of the phthalocyanine dyestufi contain at most only a few halogens, in particular a few chlorine atoms.

X is the radical of a polyalkylene polyamine containing at least one lipophilic radical and at least 3 basic nitrogen atoms, which polyalkylene polyarnine is bound at one of its N atoms to the S group, and X is the ammonium cation of such a polyalkylene polyamine, and

n and m are whole numbers the sum of which is at least 2 and at most 4, whereby m must be at least 1 and n can be 0.

X and X are derived in particular from a polyalkylene polyamine of the general Formula II 1 Q1 T Q2 f 4 I la s p R (11) Of the symbols R R R R and R at least one R represents a lipophilic radical. Advantageously, only one R and this R or R is a lipophilic radical. This is preferably a saturated, branched chain aliphatic group advantageously containing 8-16 and, particularly, 8-12 carbon atoms, advantageously the octyl, iso-octyl, decyl or dodecyl group. The lipophilic radical however can also be an araliphatic group, for example the benzyl group, which can contain saturated aliphatic substituents, e.g. a tert. butyl, tert. amyl, octyl, iso-octyl, decyl and dodecyl group. Also, if desired, the lipophilic radical can be a cycloaliphatic group, for example a cyclohexyl group. The remaining Rs advantageously represent hydrogen. However, they can also represent a lower aliphatic group, for example a methyl or ethyl group. In that part of the amine of the general Formula II corresponding to m, however, at least one R must be hydrogen.

Each of Q and Q represents a lower alkylene radical, advantageously an a,[i-alkylene radical such as, for example, the l,2-propylene radical and, preferably the 1,2- ethylene radical. However, each of Q and Q can also be an agy-alkylene radical such as, e.g. the 1,3-butylene radical and, preferably, the 1,3-propylene radical. Preferably Q =Q p represents a positive whole number, preferably 1, 2 or 3.

The new dyestulfs of the general Formula I are ob- V glycol monoethyl ether 3,057,873 Patented Oct. 9, 1962 tained by reacting one mol of a phthalocyanine compound of the general Formula III (SO'iCDm I) wherein Pc, m and n have the definitions given above and Z is hydrogen, an alkali metal or an ammonium ion, with m+n mol of a polyalkylene polyamine which contains at least one lipophilic radical and at least three basic nitrogen atoms.

This is done advantageously in aqueous suspension and possibly with the addition of inert organic solvents which are miscible with water and of acid binding agents.

Instead of a single compound of the Formulae II and III, also technical mixtures can be used, the individual components of which correspond to the Formulae II and III. In particular technical mixtures of polyalkylene polyamines of Formula II are used, preferably those which contain a portion of compounds in which R and R4, represent the same lipophilic radical and the other Rs are hydrogen.

A modification of this process for the production of the new dyestuffs of the phthalocyanine series consists in reacting 1 mol of phthalocyanine sulphonic acid chloride of the general Formula IV in which the symbols have the meanings given above, with n+m mol of polyalkylene polyamine, the reaction being performed under such conditions that a condensation product is formed which contains m mol of amine in the form of amido groups and n mol in the form of sulphonic acid ammonium salts.

This is done advantageously by reacting 1 mol of phthalocyanine sulphonic acid chloride of the general Formula IV first with m mol of polyalkylene polyamine, advantageously in aqueous suspension and with the possible addition of agents binding the hydrohalic acid, to form the corresponding sulphonic acid amide of the general Formula V wherein Pc, X m and n have the meanings given above.

'Then this product is converted into the corresponding they are easily soluble in several higher alcohols such as,

e.g. benzyl alcohol, or in several ether alcohols such as, e.g. diethylene glycol monoalkyl ethers, eg in diethylene Inks for ball point pens and stamp pads which contain dyestuffs produced according to the invention as well as solvents, are distinguished by very good fastness properties of the impressions made therewith to water, lower alkanols, acetone, ether, hydrochloric acid, caustic soda lye, aqueous ammonia, sodium hypochlorite, p0- tassium permanganate and sodium bisulphite. In addition, the inks have good fastness to light.

Such inks may possibly also contain other fast dyestuffs in order to attain the desired shade, for example, glass black.

A particularly good dyestuif according to this invention is H s(n-NH-oHT-om NH-oHT-orn -iL-R jn Po wherein:

Pc represents the radical of a metal phthalocyanine, the metal of which is a metal that has an atomic number of from 27 to 29 inclusive, i.e. including copper, nickel and cobalt,

R and R each represents a lipophilic radical selected from the group consisting of an alkyl radical containing 8 to 16 carbon atoms, a cyclohexyl radical and a benzyl radical,

n and In each represents a whole number wherein m must be at least 1 and n can be 0, the sum of n-l-m being at least 2 and at most 4, and

p and p each represents a whole number from 1 to 3 inclusive.

A dyestufi of Formula VI wherein Pc represents the radical of copper phthalocyanine and p and p each represent 1 is particularly valuable.

The following examples illustrate the invention. Parts are given therein as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is at that of grammes to cubic centimetres.

Example 1 320 parts of a mixture consisting chiefly of copper phthalocyanine monosulphonic acid-trisulphonic acid chloride (produced by known methods by heating 200 parts of copper phthalocyanine in 1600 parts of chlorosulphonic acid for 4 hours at 140), in the form of the moist filter cake are suspended in 2000 parts of ice and 1500 parts of water and the pH is quickly adjusted to 7 with dilute caustic soda lye. Then 472 parts of N -(1,1, 3,3,5,5-hexamethyl-hexyl)-diethylenetriamine, in the following termed for short tert. dodecyldiethylenetriarnine (Amine ODT produced by Monsanto Chemicals), are added and the suspension is stirred for 20 hours at 20- 25. The dyestutf is filtered off, washed with 6000 parts of water and dried in vacuo at 80. 680 parts of a soft, blue powder are obtained which is diflicultly soluble in acetone and ethanol but is up to 50% soluble in benzyl alcohol, octylene glycol or dimethyl formarnide.

If, instead of copper phthalocyanine, 200 parts of nickel or cobalt phthalocyanine are used, then dyestufis having a somewhat more green shade but otherwise similar properties are obtained.

Dyestuffs having very similar properties are obtained if, instead of 472 parts of tert. dodecyl diethylenetriamine, 324 parts of cyclohexyl diethylenetriamine, 400 parts of 3,5,S-trimethylhexyldiethylenetriamine, 376 parts of noctyl diethylenetriamine, 376 parts of Z-ethylhexyl diethylenetriamine, 425 parts of decyl diethylenetriamine, 545 parts of n-dodecyl triethylene tetramine, 605 parts of n-tetradecyl tetraethylenepentamine or 335 parts of henzyl diethylene triamine are used.

Example 2 9.5 parts of a mixture consisting chiefly of copper phthalocyanine monosulphonic acid-trisulphonic acid chloride (produced as described in Example 1), are suspended, in the form of a moist paste, in 100 parts of ice and 50 parts of water. The pH is adjusted quickly to 7 with dilute caustic soda lye and the suspension is stirred at 20-25 with a solution of 12.2 parts of tetradecyl diethylenetriamine in 50 parts of acetone. After 1 hour, 20 parts of 2 N-sodium carbonate solution are added. After stirring for another 10 hours at 20-25, the dyestuti is filtered off, washed with water and dried at in vacuo. 30 parts of a blue dyestuff are obtained which dissolves very well in benzyl alcohol or in dimethyl formamide.

If, instead of 12.2 parts of tetradecyl diethylenetriamine, 13.6 parts of hexadecyl diethylenetriamine are used, then a dyestuff having very similar properties is obtained.

Example 3 15.3 parts of a mixture consisting chiefly of copper phthalocyanine monosulphonic acid-monosulphonic acid chloride (produced by a known method by heating parts of copper phthalocyanine in 800 parts of chlorosulphonic acid for 2 hours at in the form of the moist filter cake are pasted in 100 parts of ice and 100 parts of water, and the pH is quickly adjusted to 7 with dilute caustic soda lye. Then 11 parts of tert. dodecyl triethylenetetramine dissolved in 50 parts of acetone are added and the suspension is stirred for 14 hours at 20. The dyestufi is then filtered off, washed with water and dried. It is a blue powder, of which 22. parts are obtained, which dissolves with difficulty in ethanol and acetone but easily dissolves in benzyl alcohol.

Dyestuffs having very similar properties are obtained if, in this example, the 11 parts of tert. dodecyl triethylenetetramine are replaced by 9.3 parts of tert. dodecyl diethylenetriamine, 12.5 parts of tert. dodecyl tetraethylenepentamine, 12 parts of tetradecyl triethylenetriamine, 6.35 parts of cyclohexyl diethylenetriamine or by 6.65 parts of benzyl diethylenetriamine or if the copper phthalocyanine is replaced by cobalt or nickel phthalocyanine. 1

Example 4 5.42 parts of tert. dodecyl diethylenetriamine and 10 parts of 2 N-sodium carbonate solution are added to a suspension of 9.8 parts of copper phthalocyanine tetrasulphonic acid chloride in 100 parts of ice and 100 parts of water. The copper phthalocyanine tetrasulphonic acid chloride is produced by a known process by heating 50 parts of copper phthalocyanine in 600 parts of chlorosulphonic acid for 4 hours at and then treating it with 50 parts of thionyl chloride at 80. After stirring for 10 hours at 20, a further 10 parts of 2 N-sodium carbonate solution are added and the suspension is stirred for 2 hours at 90. After cooling to 25, 5.42 parts of tert. dodecyl diethylenetriamine are added. After stirring for 1 hour at 25, the dyestuif is filtered off, washed with water and dried. 19 parts of a blue powder are obtained which dissolves well in benzyl alcohol and diethylene glycol monoethyl ether.

A dyestuif having very similar properties is obtained if the first time 4.5 parts and the second time 8 parts of tert. dodecyl diethylenetriamine are used or if both times or only the second time 4.58 parts of 3,5,5-trimethylhexyl diethylenetriamine or 4.2 parts of 2-ethylhexyl diethylenetriamine are used.

Example 5 The suspension of 19.6 parts of copper phthalocyanine tetrasulphonic acid chloride in 200 parts of ice and 100 parts of water is stirred, at pH 7, for 20 hours at 20 with 27.1 parts of tert. dodecyl diethylenetriamine. The dyestuff is filtered off, washed with water and dried at 80. 40 parts of a blue dyestuif are obtained which does not dissolve well in ethanol and acetone but dissolves well in benzyl alcohol.

A dyestuff having similar properties is obtained if, instead of the 27.1 parts of tert. dodecyl diethylenetriamine, 24.3 parts of n-decyl diethylenetriamine are used.

3,057,873 6 Example 6 are dissolved at 120 in 12 parts of octylene glycol and 38 parts of benzyl alcohol. When used as an ink for cyanine monoand di-sulphonic acid-monoand di-sul- P Point this deep blue Sohmon produces a Pi impression WhlCh has very good fastness to water, spirits,

phonic acid chloride (produced by heating 100 parts of copper phthalocyanine in 700 parts of chlomsulphovnic 5 zizleztlcfine, hypochlorite, permanganate, bisulphite, acid and acid and parts of monohydrate for 2 hours at 140),

19 parts of a mixture consisting of copper phthaloin the form of the moist paste, are suspended in 200 parts Example 10 of ice and 100 parts of water and the pH is quickly ad- 20 parts of the dyestufi produced according to Example justed to 7. 28.5 parts of dodecyl monopropylene mono- 3 from tert. dodecyl triethylenetetramine and copper ethylenetriamine are added to the suspension. After 10 phthalocyanine monosulphonic acid-monosulphonic acid stirring for 10 hours at 30, the dyestuif is filtered off, chloride and 20 parts of Kunstharz SK (ketone resin washed with water, dried and isolated whereupon 30 made by Chem. Werke Hiils, Westphalia, Germany) are parts of a blue dyestufi are obtained which dissolves well dissolved in 20 parts of octylene glycol and 60 parts of in benzyl alcohol, octylene glycol and diethylene glycol triethylene glycol at 100. Used as an ink for ball monoethyl ether. point pens, the very stable deep blue solution produces A dyestufi having the same properties is obtained if the blue impressions the general fastness properties for docu- 28.5 parts of dodecyl monopropylene monoethylenernentary purposes of which are very good.

triamine are replaced by 29.9 parts of dodecyl dipropyl- What we claim is:

enetriamine. I. A Water-insoluble phthalocyanine dyestuif of the Dyestutfs of a green shade but otherwise having very formula similar properties are obtained by replacing the copper phthalocyanine by cobalt or mckel phthalocyamne. SOrNH CH OHz 1 u' Example 7 In 19 parts of a mixture consisting chiefly of nickel phthalocyanine monosulphonic acid-trisulphonic acid chlo- ,l

ride (produced by heating 50 parts of nickel phthalo- /p cyanine in 350 parts of chlorosulphonic acid for 4 hours at 140), are suspended in 100 parts of ice and 100 parts Wherelh PC 15 the radlcal of metal p y h the of Water and the pH is quickly adjusted to 7 with caustic metal of which is Selected from the group coflsistihg'qf soda lye. A solution of 31.3 parts of N -dodecyl-N PP nickel and 6013812 R and P 9 is a p P propyl diethylenetriamine in 100 parts of acetone is added Tadlcal Selected "from the group collslshng of alkyl Wlth to the suspension. After stirring for 10 hours at 20, 8 to 16 carbon atoms, cyclohexyl yL and m the dyestufl is filtered ofi, washed with water and dried. each represents a whole number, m belng a least 1 a d 30 parts of a blue powder are obtained which dissolves Sum of belng at least 2 and at 1110512 and Well in benzyl alcohol. I) and p each represents a Whole number from 1 to 3 A dyestufi having similar properties is obtained if, inillchlslvetead 0f the 31-3 parts of N -d0decyl-N -pr0py1 djethyl- V 2. A water-msoluble phthalocyanine dyestulf of the enetriamine, 28.3 parts of N ,N -dibenzyl diethylenetriformula 32 parts of a mixture consisting chiefly of copper phthalocyanine monosulphonic acid-trisulphonic acid Pc chloride (produced as in Example 1), 1n the form of the Es0a-NHr-OHz0H:NHOHa-0 2NR:l

moist filter cake is suspended in 200 parts of ice and 150 parts of water and the pH is quickly adjusted to 7 with dilute caustic soda lye. 21.3 parts of n-decyl diethwherein Pc represents the radical of copper phthalocyanine ylene riamine and 20 p r s of methylhexyl diand R and R each represents a lipophilic radical selected ethylenetriamine are added and the suspension is stirred from the group consisting of alkyl with 8 to 16 carbon for 20 hours at The dyestllfi is filtered 1 atoms, cyclohexyl and benzyl, and n and m each reprewashed with 800 parts of Water and dried at 80. 6 sents a whole number, being at least 1 and the sum of parts of a sofit blue powder are obtained which dissolves n'+ml being t least 2 d t st 4,

up to 50% in benzyl alcohol or dimethyl formamide but 3. The water-insoluble phthalocyanine dystuif of the is difficultly soluble in acetone and ethanol. formula If, in the above example, instead of the 21.3 parts of wherein Pc represents the radical of copper phthalocyan-decyl diethylenetriamine, 25 parts of n-decyl triethylenenine. tetramine are used and if, instead of 20 parts of ,5,5- 4. The water-insoluble phthalocyanine dystufi of the trimethylhexyl diethylenetriamine, 27.6 parts of 3,5,5- for la trimethylhexyl tetraethylenepentamine are used, then a i dyestufi having similar properties is obtained. ESOPNH CHZ OH2 NH OH2 CHPN HCIOH2I Example 9 P0 30 parts of the dyestuif produced according to Example 1 from tert. dodecyl diethylenetriamine and copper phthal- 0s'N s0HzOHz-NH-OHrOHr-N-nOmEr ocyanine monosulphonic acid-trisu-lphonic acid chloride,

'2 8 wherein Pc represents the radical of copper phthalocya- 6. The water-insoluble phthalocyanine dyestufi of the nine. formula I? 02115 /SOaNH-CHr-CHzNHCHzCHr-NCHg-lH-CHr-CHr-CHr-CH; l Pe 5. The water-insoluble phthalocyanine dystufr' of the wherein Pc represents the radical of copper phthalocyaformula nine.

wherein Pc represents the radical of copper phthalocya- 25 No references cited. nine. 

1. A WATER-INSOLUBLE PHTHALOCYANINE DYESTUFF OF THE FORMULA 